Molecular Design of New Polymers Having Pendant Acidic Saccharide Moieties and Its Drug Release

天然存在的聚合物和它们的复合材料已被再次注意到作为有用的生物可降解或生物医学材料。各种多组分材料已被制备从多糖和它们的重复单元，单糖。由于D-葡糖醛酸作为多糖的组分广泛存在于动物和植物中，并且其内酯是可商购的，因此将其用作合成具有D-葡糖醛酸基侧基的新型两亲聚合物的起始材料。本论文首先合成了苯乙烯基和甲基丙烯酰基两种新型单体，分别作为可聚合官能团。苯乙烯型和甲基丙烯酰基型单体的自由基聚合及其与苯乙烯在水或二甲基亚砜中的共聚反应在60 ℃下均相进行，高产率地得到无色粉末状聚合物。通过在三氟乙酸与水（2/1，v/v）的混合物中脱保护，所得聚合物中的葡萄糖呋喃糖醛酸基部分转化为具有吡喃糖环的部分。脱保护聚合物的溶解度被发现是不同的保护聚合物在各种溶剂中。另一个新的苯乙烯型单体具有对硝基苯基在异头位置作为药物模型也被制备从D-葡萄糖醛酸-6，3-内酯。其与丙烯酰胺自由基共聚得到共聚物，该共聚物可用于释放测试。

Naturally occurring polymers and their composites have been noted again as useful biodegradable or biomedical materials. Various kinds of multicomponent materials have been prepared from polysaccharides and their repeating units, monosaccharides. Since D-glucuronic acid exists widely as a component of polysaccharides in animals and plants and its lactone was commercially available, it was used as a starting material for synthesis of novel amphiphilic polymers having D-glucuronyl pendants. At first, two kinds of new monomers, styryl and methacryloyl groups as a polymerizable functional group respectively, were prepared in the present work. The radical polymerization of styryl-type and methacryloyl-type monomers and their copolymerization with stirene in water or dimethyl sulfoxide proceeded in a homogeneous phase at 60ﾟC and gave colorless powdery polymer in high yield. Through the deprotection in a mixture of trifluoroacetic acid with water (2/1, v/v), the glucofuranuronyl moiety in the resulting polymers was converted to that having a pyranose ring. Solubility of deprotected polymers was found to be different from that of protected polymers in various solvents. Another new stryl-type monomer having p-nitrophenyl group at the anomeric position as a drug model was also prepared from D-glucurono-6,3-lactone. Its radical copolymerization with acrylamide gave a copolymer, which was useful for the release tests.